Crystal structure of bis(4-benzoyl-pyridine-κN)bis(methanol-κO)bis(thio-cyanato-κN)nickel(II) methanol monosolvate.

Carsten Wellm,Christian Näther

doi:10.1107/s2056989019001555

Carsten Wellm, Christian Näther

Open Access

https://doi.org/10.1107/s2056989019001555

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Abstract

The asymmetric unit of the title compound, [Ni(NCS)2(C12H9NO)2(CH3OH)2]·CH3OH, comprises one NiII cation, two thio-cyanate anions, two 4-benzoyl-pyridine coligands, two coordinating, as well as one non-coordinating methanol mol-ecule. The NiII cation is coordinated by two terminally N-bonded thio-cyanate anions, the N atoms of two 4-benzoyl-pyridine coligands and the O atoms of two methanol ligands within a slightly distorted octa-hedron. Individual complexes are linked by inter-molecular O-H⋯S hydrogen bonding into chains parallel to [010] that are further connected into layers parallel to (10) by C-H⋯S hydrogen bonds. Additional C-H⋯O hydrogen-bonding inter-actions lead to the formation of a three-dimensional network that limits channels extending parallel to [010] in which the non-coordinating methanol mol-ecules are located. They are hydrogen-bonded to the coordinating methanol mol-ecules. X-ray powder diffraction revealed that the compound could not be prepared as a pure phase.

Highlights

Thiocyanate anions are versatile ligands that can coordinate to metal cations in different manners, leading to a variety of structural set-ups
In the majority of cases, the metal cations are linked by thiocyanate anions into chains, but there are examples where layer formation is observed (Suckert et al, 2016; Wellm et al, 2018; Neumann et al, 2018a)
The crystal structure of the title compound consists of discrete complexes in which the NiII cations are sixfold coordinated by two crystallographically independent thiocyanate anions, two methanol molecules and two 4-benzoylpyridine ligands (Fig. 1)

Summary

Chemical context

Thiocyanate anions are versatile ligands that can coordinate to metal cations in different manners, leading to a variety of structural set-ups. With respect to paramagnetic transition metal cations, the -1,3-bridging mode is of special importance because it can mediate the magnetic exchange (Gonzalez et al, 2012; Wohlert et al, 2013a,b; Palion-Gazda et al, 2015; Guillet et al, 2016; Mekuimemba et al, 2018) In this context, an increasing number of compounds with different magnetic properties are being reported (Wohlert et al, 2014a,b; Werner et al, 2015; Suckert et al, 2017a; Mautner et al, 2018). No discrete decomposition steps are observed because all co-ligands are removed in one step Under these circumstances, alternatives are required that are based on precursor complexes comprising only two of the pyridine derivatives as ligands and two coordinating and volatile molecules such as water or methanol. This sample is still contaminated with Ni(NCS)2(4-benzoylpyridine), and any attempt to completely index its powder pattern failed (Fig. S2 in the supporting information)

Structural commentary

Supramolecular features

Database survey

Synthesis and crystallization